Neodymium-catalyzed polybutadienes

ABSTRACT

The invention relates to a high-molecular-weight, linear, neodymium-catalysed polybutadiene having a high proportion, &gt;95%, of cis-1,4 units having a low proportion, &lt;1%, of 1,2-vinyl content, and also having a small molar-mass-polydispersity index (MPI), characterized in that 
     Mooney viscosity (ML 1+4 100° C.) of the polybutadiene is from 70 to 90 and 
     The molar-mass-polydispersity index of the polybutadiene is smaller than 10.

This application is a continuation of pending U.S. patent applicationSer. No. 13/500,440 filed May 3, 2012, a nationalized application ofInternational Patent Application Serial No. PCT/EP2010/065461 filed Oct.14, 2010, claiming priority to European Patent Application No.EP09173297.4 filed Oct. 16, 2009, all incorporated herein by reference.

The present invention relates to a high-molecular-weight, linear,neodymium-catalysed polybutadiene having a high proportion, >95%, ofcis-1,4 units and having a low proportion, <1%, of vinyl units, and alsohaving a small molar-mass-distribution index (MDI), and to processes forproducing these and to use thereof.

Polybutadienes are used as important constituents of rubber mixtures inthe tyre industry, and it is desirable here to improve final properties,for example to reduce rolling resistance and abrasion. Anotherapplication sector is provided by golf-ball cores or shoe soles, wherehigh rebound resilience is a prime concern.

Polybutadienes having a high proportion of cis-1,4 units have beenproduced for a long time on a large industrial scale, and are used forproducing tyres and other rubber products, and also for impact-modifyingpolystyrene.

The current method of achieving high proportions of cis-1,4 units is thealmost exclusive use of catalysts based on compounds of the rare earths,these catalysts being described by way of example in EP-A1 0 011 184 andEP-B-A1 0 007 027.

It is known from the prior art that, among the group of the high-cispolybutadienes, specifically neodymium-catalysed polybutadienes haveparticularly advantageous properties in respect of rolling resistance,abrasion and rebound resilience.

The person skilled in the art is aware that production of polybutadieneswith low polydispersity is achieved by using structurally definedsingle-site catalysts based on ally complexes of the rare earths, thesebeing described by way of example in Macromolecular Chemistry andPhysics, 2002 (203/7) 1029-1039.

The catalyst systems used play an important part in the production ofpolybutadienes.

By way of example, the neodymium catalyst used in industry is aZiegler/Natta system, which is formed from a plurality of catalystcomponents. Formation of the catalyst mostly involves formation ofdiffering catalyst centres, and these can be discerned in an at leastbimodal molar-mass distribution within the polymer. The known 3 catalystcomponents in the Ziegler/Natta catalyst system, mostly composed of aneodymium source, a chloride source and an organoaluminium compound, aremixed in a very wide variety of ways under certain temperatureconditions, and the catalyst system here is prepared, with or without anageing process, for the polymerization reaction.

The prior art reveals a plurality of production processes forZiegler/Natta catalyst systems used for producing polybutadienes.

EP 0 375 421 B1 describes a process for producing a catalyst forpolymerizing butadiene, where an aluminium hydrocarbyl or aluminiumhydrocarbyl hydride, neodymium neodecanoate or neodymium naphthenate,and a halogen source, are mixed in solution in a hydrocarbon (hexane) ata temperature of from −15° C. to −60° C., and the catalyst system hereis aged for a period of at least 8 hours before it is used for thepolymerization reaction. The ageing process is preferably carried at−20° C.

U.S. Pat. No. 5,686,371 discloses a process for polymerizing one or moreconjugated dienes by forming the catalyst system via mixing of a salt ofa rare earth, an organoaluminium compound and a silicon halide ororganosilicon halide in the presence of a diene at a temperature of from0 to 30° C. The catalyst is then aged at room temperature before it isused for the polymerization reaction.

WO 02/068484 describes a process in which the known catalyst components,as described above, are directly introduced at a temperature of from−20° C. to 80° C., without any prior preformation process, into abutadiene-hexane solution, and the polymerization reaction takes placein a continuous process.

EP 1 055 659 describes a process for producing neodymium neodecanoatewith high water content, above 10 000 ppm, as catalyst constituent forthe solution polymerization of butadiene, where the said neodymiumdecanoate is combined with an alkylaluminium compound or hydridederivatives thereof, preferably diisobutylaluminium hydride (DIBAH), ata temperature of from 0 to 18° C. tert-Butyl chloride, as chloridesource, is added at room temperature. The ageing process lasts for 30minutes at the same temperature, before these materials are used for thepolymerization reaction.

EP 0 076 535 likewise describes the production of a neodymium catalyst,where the known catalyst components are combined at a temperature of 80°C. tert-Butyl chloride is used as chlorine component. Ageing ismentioned, without any explicit statement of the ageing conditions.

EP 0 127 236 is likewise known from the prior art, and here the catalystis produced via mixing of neodymium oxides, neodymium alcoholates andcarboxylates with an organometallic halide, and also with an organiccompound, at a temperature of from 20° C. to 25° C. It is also possibleto carry out the mixing of the said 4 components at from 50° C. to 80°C. In this variant, the mixture is cooled to from 20 to 25° C., and thenDIBAH is added. Ageing is not mentioned.

EP 1 176 157 B1 discloses a process for producing polybutadienes withreduced solution viscosity/Mooney viscosity ratio, where a preformationprocess is used during catalyst production. Here, the neodymiumversatate is first mixed with DIBAH and isoprene at 50° C., and the saidmixture is then cooled to 5° C., and then ethylaluminium sesquichloride(EASC) is added. The ageing period, at a temperature of from 10 to −80°C., can be from a plurality of minutes to a plurality of days.Comonomers, an example being a bisdiene, are added during thepolymerization reaction in order to increase the degree of branching ofthe polymer and also therefore to obtain the very narrow solutionviscosity/Mooney viscosity ratio. By virtue of the coupling by way ofthe bisdiene, the resultant branched polymer has at least 4 free chainends per molecule, whereas linear molecules possess only 2 chain ends.

The number of chain ends within the polymer has a positive correlationwith energy dissipation. As the number of free chain ends increases, theamount of energy dissipation via the polymer increases. However, as theamount of energy dissipated by the polymer decreases, rolling resistancedecreases and the rebound resilience of the polymer improves, forexample. Accordingly, the final properties of a linear polymer havingonly 2 chain ends per molecule are always better than those of abranched polymer, for identical molar mass.

Polymers having high molar mass are moreover preferable to polymershaving low molar mass.

It is known that the number-average molar masses Mn of commerciallyavailable polybutadienes are normally from 150 000 to 400 000 g/mol. Theactual molar-mass distribution of the polymer is mostly shown in a GPCcurve and extends over a very large region, which mostly extends wellbeyond a 10-fold difference.

Number-average molar masses Mn below 100 000 g/mol are particularlydisadvantageous, since statistically, because of their small molar mass,they give poor binding into the polymer network, thus additionallyimpairing energy absorption, where this results from an increased levelof free movement of the entire polymer chain.

In contrast, number-average molar masses Mn above 1 000 000 g/molexponentially increase the solution viscosity of the polymer; thesolubility of the polymer is therefore reduced. A disadvantage of highmolar masses is therefore that cost-effective production of the saidpolymers becomes more difficult.

This is because in the absence of the said high-molecular-weightfractions within the polymer the amount of deposit on the walls of thereactor is reduced, i.e. less gel is formed, and reactor operating timecan therefore be longer. Maintenance and cleaning of the reactors istherefore minimized, and this saves time and expense.

It is known that commercially produced polymers have statisticalmolar-mass distribution, the breadth of the molar-mass distributionbeing influenced by the catalyst-production process.

It was therefore the object according to the invention to provide alinear polybutadiene of high molecular weight which by virtue of lowsolution viscosity can provide an easy production process in thepolymerization reaction, while also having an advantageous effect on theservice properties of the rubber by virtue of a polymer structure whichis uniform, linear, and of high molecular weight.

A polybutadiene of the type mentioned in the introduction is proposed inorder to achieve the object, its Mooney viscosity (ML₁₊₄100° C.) beingfrom 70 to 90, and its molar-mass-distribution index (MDI) being <10.

It is preferable that these polybutadienes have been catalysed byneodymium-containing systems. Systems of this type are Ziegler-Nattacatalysts based on neodymium compounds which are soluble inhydrocarbons.

The neodymium compound used particularly preferably comprises neodymiumcarboxylates or neodymium alcoholates, in particular neodymiumneodecanoate, neodymium octanoate, neodymium naphthenate, neodymium2,2-diethylhexanoate and/or neodymium 2,2-diethylheptanoate

It is known that excellent properties in tyre mixtures, e.g. low rollingresistance, high rebound resilience or low tyre abrasion, are obtainedby minimizing polydispersity (PDI). Polydispersity is generallydetermined by gel permeation chromatography (GPC); it is the quotientobtained by dividing weight-average molar mass Mw by number-averagemolar mass Mn, and therefore represents the breadth of molar-massdistribution.

Broad molar-mass distribution is seen in good processing behaviour ofthe rubber and rubber mixtures, and this is seen inter alia inrelatively low mixture viscosity, relatively small mixing time, andrelatively low extrusion temperatures. However, there is an adverseeffect on the property profile of the tyre.

Low polydispersity accordingly has the opposite effect on the processingbehaviour of the abovementioned polybutadiene.

However, it has been found that the PDI index does not provide anadequate description of the actual properties of the polymer. Inparticular, no information is provided about the marginal regions of themolar-mass distribution, since the PDI merely provides a quotientcalculated from the weight-average and number-average molar masses.

The molar-mass-distribution index (MDI) has therefore been introducedaccording to the invention, and is determined from gel permeationchromatography; it is the quotient obtained by dividing Mw (90%) by Mw(10%), and therefore describes the final property of the polymer. Asmall MDI, <10, means that the molar-mass distribution of the polymer isvery narrow, and therefore that a uniform network structure can beformed.

The polybutadiene according to the invention therefore has the desiredexcellent properties in tyre mixtures.

The 1,4-cis content of the polybutadiene according to the inventionis >95%, preferably >96%, and its 1,2-vinyl content is <1%, preferably<0.8%, particularly preferably <0.7%.

The solution viscosity (RT, 5.43%, toluene) of the polybutadieneaccording to the invention is preferably from 350 to 630 mPas, withpreference from 400 to 580 mPas.

It is moreover preferable that the branching index (BD of thepolybutadiene according to the invention is from 5 to 7. The BI is thequotient obtained by dividing solution viscosity by Mooney viscosity. Itis known that, for polymers of identical structure, solution viscosityincreases proportionally as Mooney viscosity increases. If the increaseis subproportional, i.e. if BI is smaller than 5, solution viscosity isreduced by polymer branching, and this reduces the linearity of thepolymer and increases the undesired number of free chain ends. Anysuperproportional increase, i.e. BI greater than 7, is mostly broughtabout by an increased number of very high-molecular-weight polymerchains, and makes production of the polymer more difficult.

The Mooney relaxation of the polybutadiene according to the invention ismoreover preferably smaller than 6% after 30 sec. Mooney relaxation isbrought about by slippage of the polymer chains after dynamic stressingof the polymer after the end of the Mooney measurement process, andindicates the linearity of the polymer.

The molar-mass distribution of the polybutadiene according to theinvention is Mw 90%<1 000 000 g/mol and Mw 10%>100 000 g/mol. Thismolar-mass distribution is ideal for the polybutadiene according to theinvention, since, as described above, it provides easy production and atthe same time guarantees the desired good final properties of thepolymer.

The polybutadiene according to the invention not only has improvedrolling resistance and increased rebound resilience, but also is easierto produce, because it is associated with less deposition on the wallsof the reactor, and less gelling, and therefore longer operating time ofthe reactor. Maintenance of the reactors is thus minimized, and thissaves time and expense.

The polybutadiene according to the invention has other advantages duringthe production process, during transport, and during storage andprocessing, and also has the characteristics required for use in golfballs or in tyre production.

A further invention is a process for producing the polybutadieneaccording to the invention, by carrying out the following steps:

1. modified catalyst production using a preformation process, with useof catalyst systems based on neodymium, composed of

-   -   component A: an alcoholate or a carboxylate of neodymium,        preferably neodymium versatate,    -   component B: a dialkylaluminium hydride, preferably        diisobutylaluminium hydride (DIBAH),    -   component C: a trialkylaluminium compound, preferably        tributylaluminium (TIBA),    -   component D: a diene, preferably butadiene or isoprene, and    -   component E: at least one organometallic halide, preferably        ethylaluminium sesquichloride (EASC),    -   where, in a first step, components A, B, C and D are firstly        mixed at a temperature of from 0° C. to 80° C., preferably from        30° C. to 60° C., for a period of from 5 minutes to 10 hours,        preferably from 20 minutes to 2 hours, and the mixture is then        cooled to below -10° C., preferably to below -30° C., prior to        addition of component E;

2. a process of preformation of the modified catalyst system at atemperature of from −30° C. to 80° C., preferably from 5° C. to 50° C.,for a period of from 1 to 250 hours, preferably from 2 to 100 hours;

3. polymerization of the monomers at a temperature of from −20 to 150°C.

By conducting the process according to the invention, it was possible toform a catalyst system which is based on neodymium and which has idealactivity, and which leads to the desired abovementioned properties ofthe polymer. The final properties of the polymer and thecost-effectiveness of the production process are functions of the amountand mode of action of the catalyst constituents. If, for example, theamount of catalyst used is too small, although the molar mass rises, andthe Mooney viscosity of the polymer therefore rises, there is acorresponding slowing of the reaction of the monomer, and this isundesirable for economic reasons.

It is surprising that the modification, namely the lowering of thetemperature for mixing of catalyst components A to D prior to additionof the chloride source E, with the additional collaborative effect ofcatalyst DIBAH as component B, and TIBA as component C, permittedformation of a catalyst system which has ideal activity and which isdecisive for obtaining the polybutadiene according to the invention,with the abovementioned properties.

It is preferable that component D is a monomer identical with that usedfor producing high-molecular-weight neodymium-catalysed polybutadienes.The presence of the diene during catalyst production is particularlyimportant, since it permits formation of a stable catalyst complex. Thesolvent used can comprise hexane, cyclohexane, toluene, or a solventmixture of the C6 fraction. It is equally possible to use othersolvents.

The solvent can be added in pure form or in the form of solvents of theindividual catalyst components. The amount of solvent depends oncomponent A, where the concentration of component A with respect to thesolvent is from 0.05 to 0.3 mol/L, preferably from 0.08 to 0.2 mol/L.

The molar ratio of component A to component B is from 1:1 to 1:100,preferably from 1:3 to 1:80 and particularly preferably from 1:3 to1:50, the molar ratio of component A to component C is from 1:0.4 to1:15, preferably from 1:0.5 to 1:8, the molar ratio of component A tocomponent D is from 1:1 to 1:200, preferably from 1:2 to 1:100 andparticularly preferably from 1:3 to 1:50, and the molar ratio ofcomponent A to component E is from 1:0.5 to 1:20, preferably from 1:0.7to 1:10 and particularly preferably from 1:0.8 to 1:8.

The cooling temperature in step 1 of the modified catalyst productionprocess is preferably −10° C. or −20° C., preferably −30° C.,particularly preferably −60° C. It is surprising that the said step hasled to a catalyst system with which the polybutadiene according to theinvention can be produced.

The invention further provides rubber mixtures comprising apolybutadiene according to the invention.

After the catalyst system has been preformed, the polymerizationreaction is carried out in organic solvents. These solvents must beinert in relation to the catalyst system used. By way of example,aromatic, aliphatic and cycloaliphatic hydrocarbons are suitable,examples being benzene, toluene, pentane, n-hexane, isohexane, heptaneand cyclohexane.

The polymerization reaction can be carried out either continuously orbatchwise.

The polymerization reaction is carried out at a temperature of from −20to 150° C., preferably from 0 to 120° C.

In one usual embodiment, the catalyst composed of components A, B, C, Dand E is added to a mixture of 100 parts by weight of solvent with from5 to 50 parts by weight, preferably from 8 to 30 parts by weight, ofmonomer.

Once the desired conversion has been reached, the catalyst isdeactivated via addition of small amounts of, for example, water,carboxylic acids or alcohols.

Usual amounts of usual stabilizers can be added to the polymer solution,prior to work-up. Examples of stabilizers used are sterically hinderedphenols or aromatic amines or phosphites, e.g.2,6-di-tert-butyl-4,5-methylphenol.

The polymers are isolated via evaporation to concentrate the polymersolution, via precipitation by a non-solvent, such as methanol, ethanol,or acetone, or preferably via steam-distillation of the solvent.

After the steam-stripping process, water is removed by using suitablesieving assemblies or suitable assemblies comprising screws, examplesbeing expeller screws and expander screws, or by using a fluidized-beddryer.

The usual processes are used for drying, for example in a drying cabinetor in a screw-conveyer dryer.

The polybutadienes according to the invention can be used alone, in ablend with aromatic or aliphatic oils, or in a mixture with otherrubbers. Suitable additional rubbers for producing rubber vulcanizatesare not only natural rubber but also synthetic rubbers. Examples ofpreferred synthetic rubbers are described, in W. Hofmann,Kautschuktechnologie [Rubber Technology], Gentner Verlag, Stuttgart 1980and I. Franta, Elastomers and Rubber Compounding Materials, Elsevier,Amsterdam 1989. They encompass inter alia

BR—conventional polybutadiene

ABR—butadiene/C1-C4-alkyl acrylate copolymers

CR polychloroprene

IR polyisoprene

SBR—styrene/butadiene copolymers having styrene contents of from 1 to60% by weight, preferably from 20 to 50% by weight

IIR isobutylene/isoprene copolymers

NBR butadiene/acrylonitrile copolymers having acrylonitrile contents offrom 5 to 60% by weight, preferably from 10 to 40% by weight

HNBR—partially hydrogenated or fully hydrogenated NBR rubber

EPDM—ethylene/propylene/diene copolymers

and mixtures of the said rubbers. Materials of interest for theproduction of motor vehicle tyres are in particular natural rubber,emulsion SBR, and also solution SBR rubbers with glass transitiontemperature above −50° C., which may, if appropriate, have modificationby silyl ethers or by other functional groups, as described in EP-A-0447 066, polybutadiene rubber having high 1,4-cis content (>90%),produced by using catalysts based on Ni, Co, Ti or Nd, and alsopolybutadiene rubber having vinyl content of from 0 to 75%, and alsomixtures of these.

The invention further provides the rubber mixtures, which generallycomprise from 5 to 300 parts by weight of an active or inert filler,e.g.

-   -   fine-particle silicas, produced by way of example via        precipitation from solutions of silicates, or flame hydrolysis        of silicon halides with specific surface areas of from 5 to 1000        m²/g, preferably from 20 to 400 m²/g (BET surface area) and with        primary particle sizes of from 10 to 400 nm. The silicas can, if        appropriate, also take the form of mixed oxides with other metal        oxides, such as the oxides of Al, of Mg, of Ca, of Ba, of Zn, of        Zr, or of Ti,    -   synthetic silicates, such as aluminium silicate, or alkaline        earth metal silicate, such as magnesium silicate or calcium        silicate, with BET surface areas of from 20 to 400 m²/g and        primary particle diameters of from 10 to 400 nm,    -   natural silicates, such as kaolin and any other naturally        occurring form of silica,    -   glass fibres and glass-fibre products (mats, strands), or glass        microbeads,    -   metal oxides, such as zinc oxide, calcium oxide, magnesium        oxide, aluminium oxide,    -   metal carbonates, such as magnesium carbonate, calcium        carbonate, zinc carbonate,    -   metal hydroxides, e.g. aluminium hydroxide, magnesium hydroxide,    -   metal salts, e.g. the zinc or magnesium salts of        [alpha],[beta]-unsaturated fatty acids, e.g. acrylic or        methacrylic acid, having from 3 to 8 carbon atoms, examples        being zinc acrylate, zinc diacrylate, zinc methacrylate, zinc        dimethacrylate, and mixtures thereof;    -   carbon blacks. The carbon blacks to be used here are those which        are produced by lamp-black process, furnace-black process or        gas-black process and which have BET surface areas of from 20 to        200 m²/g, examples being SAF, ISAF, HAF, FEF or GPF carbon        blacks,    -   rubber gels, in particular those based on polybutadiene,        butadiene/styrene copolymers, butadiene/acrylonitrile copolymers        and polychloroprene.

Particular preference is given to zinc diacrylates, and fine-particlesilicas and carbon blacks.

The fillers mentioned can be used alone or in a mixture. In oneparticularly preferred embodiment, the rubber mixtures comprise, asfillers, a mixture of pale-coloured fillers, e.g. fine-particle silicas,and of carbon blacks, where the ratio of pale-coloured fillers to carbonblacks in the mixture is from 0.05 to 20, preferably from 0.1 to 10.

The form in which the fillers are added to the solution of thepolybutadienes according to the invention is preferably that of solidsor of slurry in water or in a solvent. The rubber solution can beproduced in advance, but it is preferable that the solution derivingfrom the polymerization reaction is used directly. The solvent is thenremoved thermally or preferably with the aid of steam. The conditionsfor the said stripping process can easily be determined throughpreliminary experimentation.

Preference is further given to addition of the fillers to the solidpolybutadiene according to the invention or to a mixture of rubbers, andincorporation by mixing in a known manner, e.g. by using a kneader.

The rubber mixtures according to the invention also comprisecrosslinking agents, if appropriate. Crosslinking agents used cancomprise sulphur or peroxides, and sulphur is particularly preferredhere. The rubber mixtures according to the invention can comprisefurther rubber auxiliaries, such as reaction accelerators, antioxidants,heat stabilizers, light stabilizers, antiozonants, processing aids,plasticizers, tackifiers, blowing agents, dyes, pigments, waxes,extenders, organic acids, retarding agents, metal oxides, and alsoactivators, e.g. triethanolamine, polyethylene glycol, hexanetriol,etc., these being known to the rubber industry.

In the preferred rubber mixtures using high-activity precipitatedsilicas, it is particularly advantageous to use additional filleractivators. Preferred filler activators are sulphur-containing silylethers, in particular bis(trialkoxysilylalkyl) polysulphides, asdescribed in DE-A-2,141,159 and DE-A-2,255,577, oligomeric and/orpolymeric sulphur-containing silyl ethers of DE-A-4,435,311 and EP-A-0670 347, and mercaptoalkyltrialkoxysilanes, in particularmercaptopropyltriethoxysilane and thiocyanatoalkyl silyl ether, e.g. asdescribed in DE-A-195 44 469.

The amounts used of the rubber auxiliaries are usual amounts, and dependinter alia on the intended use. Examples of usual amounts are amounts offrom 0.1 to 50% by weight, based on rubber.

The further blending of the rubbers with the other rubber auxiliaryproducts mentioned, crosslinking agents and accelerators can be carriedout in the usual way with the aid of suitable mixing assemblies, such asrolls, internal mixers and mixing extruders.

The compounding and vulcanization processes are described in more detailby way of example in Encyclopedia of Polymer Science and Engineering,Vol. 4, pp. 66 ff (compounding) and Vol. 17, pp. 666 ff (vulcanization).

The rubber mixtures according to the invention can be vulcanized atusual temperatures of from 100 to 200° C., preferably from 130 to 180°C. (if appropriate under pressure of from 10 to 200 bar).

The rubber mixtures according to the invention have excellentsuitability for producing mouldings of any type.

Non-limiting examples of the said mouldings are O-rings, profiles,gaskets, membranes, tyres, tyre treads, damping elements and hoses.

Particular preference is given to various tyre components and tyretreads.

The rubber mixtures according to the invention are moreover suitable forimpact modifying thermoplastics, in particular for polystyrene andstyrene/acrylonitrile copolymers.

The rubber mixtures are particularly suitably used for golf balls, inparticular golf-ball cores.

Examples are used below for further explanation of the invention.

EXAMPLES Inventive Example 1 Polymerization of Butadiene WithCatalyst-Preformation Process Catalyst Production and PreformationProcess:

4.26 mL (24 mmol) of diisobutylaluminium hydride, 3.03 mL (12 mmol) oftriisobutylaluminium, 1.2 mL (12 mmol) of isoprene, and also 11.3 mL (3mmol) of a 0.265 molar solution of neodymium versatate, were introducedin hexane into a dry, argon-inertized Schlenk vessel. The mixture wasstirred at 50° C. for 90 min. The solution was then cooled with dry iceand when the temperature had reached −30° C. 8 mL (2 mmol) of a 0.25molar solution of ethylaluminium sesquichloride in hexane were added.The preformed catalyst solution was allowed to stand overnight at roomtemperature and was then used for the polymerization reaction.

Polymerization Reaction:

595 g of hexane (dried over molecular sieve), and also 1.12 mL (1.12mmol) of a 1 molar solution of triisobutylaluminium in hexane, 1.71 mL(0.18 mmol of Nd) of the catalyst solution described above, coming fromthe preformation process, and 124 g of butadiene were charged to a dry,argon-inertized 1.9 L glass autoclave. The mixture was heated to 65° C.and polymerized for 2 h, with stirring. 549 g of the viscous solutionwere then discharged, and 2 mL of methanol, and also 0.6 g ofbis[3-<t>butyl-2-hydroxy-5-methylphenyl]methane were incorporated bystirring. The polymer was then dried in vacuo at 70° C. Weight ofproduct after drying: 87 g

Mooney viscosity (ML 1+4 at 100 ° C.): 81 MU; ML-Relax 30 sec: 5.4%

Solution viscosity (5.43% in toluene, at room temperature): 518 mPas;BI: 6.4

Molar-mass distribution: w(10%)=122 000 g/mol; w(90%) =933 000 g/mol,

-   -   MDI: 7.6;    -   Mn: 255 000 g/mol; Mw: 487 000 g/mol.

Comparative Example 2 Polymerization Without Catalyst-PreformationProcess

555 g of hexane (dried over molecular sieve), 1.03 mL of a 1 molarsolution of diisobutylaluminium hydride in hexane, 1.67 mL of a 0.618molar solution of triisobutylaluminium in hexane, 3.45 mL of a 0.05molar solution of neodymium versatate in hexane, 3.45 mL of a 0.05 molarsolution of ethylaluminium sesquichioride in hexane, and 130 g ofbutadiene were charged to a dry, argon-inertized 1.9 L glass autoclave.The mixture was heated to 65° C. and polymerized for 2 h, with stirring.568 g of the viscous solution were then discharged, and 2 mL ofmethanol, and also 0.6 g ofbis[3-<t>butyl-2-hydroxy-5-methylphenyl]methane were incorporated bystirring. The polymer was then dried in vacuo at 70° C. Weight ofproduct after drying: 96 g

Mooney viscosity (ML 1+4 at 100 ° C.): 77 MU; ML-Relax 30 sec: 6.9%

Solution viscosity (5.43% in toluene, at room temperature): 725 mPas;BI: 9.4

Molar-mass distribution: w(10%)=85 000 g/mol; w(90%)=1 070 000 g/mol,

-   -   MDI: 12.6;    -   Mn: 199 000 g/mol; Mw: 520 000 g/mol.

Comparative Example 3 Polymerization of Butadiene WithCatalyst-Preformation Process, Without TIBA Catalyst Production andPreformation Process:

7.5 mL (42 mmol) of diisobutylaluminium hydride, 1.2 mL (12 mmol) ofisoprene, and also 11.3 mL (3 mmol) of a 0.265 molar solution ofneodymium versatate in hexane were introduced into a dry,argon-inertized Schlenk vessel. The mixture was stirred at 50° C. for 90mm. It was then cooled to 5° C., and 8 mL (2 mmol) of a 0.25 molarsolution of ethylaluminium sesquichloride in hexane were added. Thecatalyst solution coming from the preformation process was allowed tostand overnight at room temperature and was then used for thepolymerization reaction.

Polymerization Reaction:

580 g of hexane (dried over molecular sieve), 1.68 mL of the catalystsolution described above, coming from the preformation process, and 120g of butadiene were charged to a dry, argon-inertized 1.9 L glassautoclave. The mixture was heated to 65° C. and polymerized for 3 h,with stirring. 616 g of the viscous solution were then discharged, and 2mL of methanol, and also 0.6 g ofbis[3-<t>butyl-2-hydroxy-5-methylphenyl]methane were incorporated bystirring. The polymer was then dried in vacuo at 70° C. Weight ofproduct after drying: 103 g

Mooney viscosity (ML 1+4 at 100 ° C.): 44 MU; ML-Relax 30 sec: 5.2%

Solution viscosity (5.43% in toluene, at room temperature): 278 mPas;BI: 6.3

Molar-mass distribution: w(10%)=82 000 g/mol; w(90%)=783 000 g/mol,

-   -   MDI: 9.7;    -   Mn: 279 000 g/mol; Mw: 387 000 g/mol.

Testing of Mixture

For production of a compounded material, in each case the polymeraccording to the invention from Inventive Example 1 and the polymer fromComparative Example 3 is mixed with various substances and vulcanized.The physical properties of the respective compounded material are thendetermined and compared.

The substances used for the mixture studies were as follows:

Corax N 236 carbon black from KMF Laborchemie Handels GmbH, Vivatec 500oil from Hansen & Rosenthal; Zinkweiss Rotsiegel zinc oxide from GrilloZinkoxid GmbH; EDENOR C 18 98-100 stearic acid from Cognis DeutschlandGmbH; Vulkanox® 4020/LG and Vulkanox® HS/LG stabilizers, and alsoVulkacit® CZ/C rubber chemicals from Lanxess Deutschland GmbH, Antilux654 stabilizer and RHENOGRAN IS 60-75 sulphur from Rhein Chemie.

Mixture constituents in phr* Inventive Comparative (g per 100 g ofpolymer): Example 1 Example 3 Inventive Example 1 100 ComparativeExample 3 100 CORAX N 326 50 50 VIVATEC 500 4 4 EDENOR C 18 98-100 3 3VULKANOX 4020/LG 2 2 VULKANOX HS/LG 3 3 ZINKWEISS ROTSIEGEL 2 2 RESINSP-1068 3 3 ANTILUX 654 2 2 VULKACIT CZ/EGC 1.4 1.4 RHENOGRAN IS 60-752.36 2.36 *phr = parts per hundred rubber

Inventive Comparative Test Unit Example 1 Example 3 ML 1 + 4/100 MU 8052 Shore A hardness @ 60° C. 61 61 Tensile test @ 23° C. S300 MPa 5.65.3 D median % 526 514 F median MPa 14.7 13.1 Rebound resilience @ 23°C. % 62 55 @ 60° C. % 65 63 MTS Amplitude Sweep @ 60° C., 1 Hz G* (0.5%)1st measurement MPa 2.05 2.26 G* (0.5%) 2nd measurement MPa 1.98 2.13 G*(0.5%) 3rd measurement MPa 1.97 2.12 G* (15%) 1st measurement MPa 1.131.11 G* (15%) 2nd measurement MPa 1.14 1.11 G* (15%) 3rd measurement MPa1.14 1.11 tan d (max.) 1st measurement 0.16 0.181 tan d (max.) 2ndmeasurement 0.16 0.181 tan d (max.) 3rd measurement 0.16 0.180

The two compounded materials have identical hardness after vulcanizationand are therefore directly comparable. In the tensile test, InventiveExample 1 exhibits improved dynamic properties in comparison withComparative Example 3, discernible in greater tensile strength (Fmedian) and greater tensile strain (D median).

Inventive Example 1 exhibits markedly improved rebound resilience whencompared with Comparative Example 3. In the MTS test, Inventive Example1 exhibits a smaller maximum value than Comparative Example 3 for thetangent delta (tan d) loss factor, this being a sign of reduced energyabsorption by the polymer, and it is therefore possible to conclude thatrolling resistance is markedly lower in inventive Example 1 than inComparative Example 3.

What is claimed is:
 1. High-molecular-weight, linear,neodymium-catalysed polybutadiene having a high proportion, >95%, ofcis-1,4 units and having a low proportion, <1%, of 1,2-vinyl content,and also having a small molar-mass-distribution index (MDI),characterized in that Mooney viscosity (ML ₁₊₄ 100° C.) of thepolybutadiene is from 70 to 90 and the molar-mass-distribution index ofthe polybutadiene is smaller than 10 and a Mw 90%<1 000 000 g/mol and Mw10%.>100 000 g/mol.
 2. Polybutadiene according to claim 1, characterizedin that the solution viscosity (RT, 5.43%, toluene) is from 350 to 630mPas.
 3. Polybutadiene according to claim 2, characterized in that thebranching index (BI) is from 5 to
 7. 4. Polybutadiene according to claim3, characterized in that its Mooney relaxation after 30 sec (ML-Relax30sec) is smaller than 6%.
 5. Process for producinghigh-molecular-weight, neodymium-catalysed polybutadienes according toclaim 1 comprising: 1) modifying the catalyst production using apreformation process, with use of catalyst systems based on neodymium,composed of component A: an alcoholate or a carboxylate of neodymium,preferably neodymium versatate, component B: a dialkylaluminium hydride,preferably diisobutylaluminium hydride (DIBAH), component C: atrialkylaluminium compound, preferably tributylaluminium, component D: adiene, preferably butadiene or isoprene, and component E: at least oneorganometallic halide, preferably ethylaluminium where, in a first step,components A, B, C and D are first mixed at a temperature of from 0° C.to 80° C. for a period of from 5 minutes to 10 hours, and cooling themixture to below −10° C. prior to addition of component E; 2) preformingthe modified catalyst system at a temperature of from −30° C. to 80C-for a period of from 1 to 250 hours; and 3) polymerizing monomers at atemperature of from −20 to 150° C. to produce the polybutadiene. 6.Process according to claim 5, characterized in that component D is amonomer identical with that used for producing high-molecular-weightneodymium-catalysed polybutadienes.
 7. Process according to claim 6,characterized in that the molar ratio of component A to component B isfrom 1:1 to 1:100, the molar ratio of component A to component C is from1:0.4 to 1:15, the molar ratio of component A to component D is from 1:1to 1:200, and the molar ratio of component A to component E is from1:0.5 to 1:20.
 8. Rubber mixtures comprising a polybutadiene accordingto claim
 1. 9. A moulding comprising the rubber mixture of claim
 8. 10.The moulding according to claim 9, wherein the is a tire component. 11.An impact-modifying thermoplastic comprising the rubber mixtureaccording to claim
 10. 12. Polystyrene and styrene/acrylonitrilecopolymers comprising rubber mixtures according to claim
 8. 13. A golfball comprising a rubber mixture according to claim 8.